Process for producing copper oxychloride



Oct. 13, 1953 P. K. ANDERSON 2,655,432

PROCESS FOR PRODUCING COPPER OXYCHLORIDE Original Fliled March 12, 19473 Sheets-Sheet l PmUP K.ANbERsoN.

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'L'. ATToR N Eva.

Oct. 13, 1953 P K. ANDERSON 2,655,432

PROCESS InOR PRODUCING COPPER OXYCHLORIDE Original Filed March 12, 19473 Sheets-Sheet 2 mvcuvo. Pmmp K ANDE RSON.

t, AT1-o R N SYS.

Oct. 13, 1953 P. K. ANDERsoN PROCESS F'OVR PRODUCING COPPER OXYCHLORIDE3 Sheets-Sheet 3 Original Filed March 12, 1947 PHILIP K.ANDERSON.

"L; ATTORNEYS.

Patented Oct. 13, 1.49.53

PROCESS FOR PRODUCING COPPER OXYCHLORIDE Philip KennethAnderson, Rahway,N. J., assigner to The American Metal Company York, N. Y., a corporationof New Original application Marc 734,014. Divided and th,1952,.Seria1N0. 294,761

( Cl. 23g-2,03)

44 Claims.

This invention relates to `vessels or containers, and more particularlyto means for facilitating the aeration of liquids and solids containedin a vessel.

This application is a division of application Serial No. 734,014, ffiledMarch `12, 1947, now United States Patent No. 2,624,657.

My apparatus is particularly adapted to the manufacture oi complexcompounds -of copper such as copper oxychloride though not restrictedthereto. Such compounds have been produced in the past by introducingmetallic copper into a solution vof ammoniacal calcium chloride andaerating same in a reaction vessel. Copper oxychloride is but :one `ofmany complex compounds of copperfoxide and calcium chloride `which havebeen found useful, for example, as fungicides. Many attempts have beenmade to Iproduce these compounds at sufiiciently low cost to make themcommercially feasible.

The principal factor controlling the production rate of `copperoxychloride, when the latter is produced by the above mentioned processof aeration of copper in calcium chloride and ammonium chloride, hasbeen the rate of dissolution of the metallic copper. The exact `chemicalreactions involved in aerating metallic Acopper in a solution of calciumand ammonium chloride are not accurately known, but it is believed thatthe air oxidizes the copper to form copper oxychloride.

Processes and apparatus have been heretofore proposed for making copperoxychloride, for example, as shown in Haag et al. U. S. Patent2,358,706, dated September 19, 1944. I designate such material producedby said patent as copper oxychloride although vthe patentee states thatsuch compounds may be designated `for convenience of reference calciumcuproxy chlorides, although by such a designation the particularstructural formula or a particular degree of hydration -is not meanttobe ascribed. But `up to now, such attempts to make copper oxychloridehave been of restricted importance rand largely have been unsuccessfulbecause the rate of production in comparison to the size of the`investment for the equipment is so low that the unit cost of theproduct hasbeen high.

Other reaction vessels for making copper oxychloride have been proposed.They included air outlets or orifices .which did not permit propercontact between the air, `copper and reagents either because the aircurrents were not properly placed or the copper oxychloride settled onthe copper andprevented'furtherreaction.

Ltd., .N ew York h 12, 1947, Serial No. is application June 20,

According to the present invention, an ,object is to provide novelapparatus for overcoming the above difficulties.

The above and further objects and novel featudes 1will more fully appearfrom the detailed description when the same is read in connection withthe accompanying drawings. It is to be expressly understood, however,that Vthe drawings are for purposes of illustration only and are notintended as a denition ofthe limits of the invention, reference for thislatterpurpose being had to the appended claims.

In the drawings, wherein like reference characters refer to like parts`throughout .the several views:

Fig. 1 is a top plan view `of one embodiment of the invention;

Fig. 2 isa sectional vview taken on line 2--2 of Fig. 1,;

Fig. y2a .is a `vertical sectional view, `partly in section `and withparts ,broken away, `of a reaction tank illustrating 4a 'secondembodiment of the invention; and

Fig. 3 is a sectional View takenon line `3--3 of Fig. 2, showing aparticular bank of conduits for an aerating `medium at the level of line3-3, and also showing other ,banks of conduits at levels below -line 33.

The forms of the invention illustrated in the accompanying drawings, byway of example, comprise a reaction tank or vessel for the production ofcopper oxychloride wherein pieces of copper `are acted upon lby AaVcalcium chloride `and ammonium 4chloride liquor and by air. Streams of`the latter Vare directed into the Vessel at Vor near the bottom,thereof and pass in contact with the copper. The ,bottom of the novelvessel is provided with a plurality of steps which are so disposedrelative to one another that a gaseous medium such as air directed `intothe container through the sides or faces ofthe steps will ccntact freelyand effectively .any metallic Acopper situated =upon the steps. .Any`material which is capable ofsettling `to the bottom of the vessel isdirected into` direct lcontact with ythe air. With respect to metalliccopper this aids the chemical action and `dissolution thereof. Withrespect to the `precipitate (copper oxychloride) .which tends to settleas Ia slurry, .the ,novel bottom directs same into 4the aerating streamwhich recirculates it and keeps it in suspension. The novel steppedbottom of the tank may also be describedas comprising apluralityof.troughs into whichan aerating `medium -is directed through the sides orybottoms ,0f the troughs. Any material which settles 3 to the bottom isdirected by means of the troughs into direct contact with an air stream.

The concentration of the reaction liquor may vary widely. Of course, itis generally desired to maintain concentrations which will inducemaximum reaction or dissolution rates of copper. In general, in thepresent invention, a liquor is used having a gravity varying between 5and 25 Baum measured at about 20 to 30 C. The weight ratio of calciumchloride to ammonium chloride may vary from about 4 to 1 to about 6to 1. It has been found preferable to have a gravity of between 17 to 20Baume and a weight ratio of calcium chloride to ammonium chloride ofabout 5 to 1.

The rate of aeration should be the maximum possible without causingundesirable or excessive splashing. In the embodiments of the inventiondescribed herein, it has been found desirable to employ air at a rate ofbetween l0 C. F. M. to C. F. M. for each square foot of bottom area ofthe reaction vessel. More specifically about 12.5 C. F. M. are employedfor each square foot of bottom area in the present invention.

One of the disadvantages of prior reaction tanks is that large inactiveregions exist between air conduit outlets which permit the building upof metallic copper coated with slurry (settled copper oxychloride) thusdecreasing the productive capacities of the tank by decreasing the -fareas of copper exposed to the aerating stream and to the reactionliquor.

Novel means are provided in accordance with my invention for eliminatingany inactive regions and attaining a superior distribution of air atgreater uniformity than heretofore suggested. Said novel means alsoeffect a continued suspension of the product (copper oxychloride) andpromote a maximum production by continuously exposing the metalliccopper to streams of air.

I provide a novel reaction-promoting bottom surface comprising aplurality of steps preferably having inclined faces and horizontaltreads. The aerating fluid is directed preferably to sweep across thetreads. The steps preferably occupy the entire bottom of the reactiontank and any metallic copper in the tank must fall upon some one of thetreads where it is in direct contact with an air stream. The same istrue of the precipitate or slurry which may tend to settle and to coatthe metallic copper. That is, the copper oxychloride may tend to settlebut will fall upon one of said treads and be violently agitated by anair stream directed thereacross whereby it will be urged upwardly andaway from a settled condition. Thus a fouling or covering of themetallic copper by the precipitate is avoided.

In the form of the invention shown in Figs. 1, 2, 2a and 3, the novelreaction tank is constituted by a vessel which may be, for example, vefeet in depth with a diameter of 6 feet. Such a vessel is indicated atI0 in the accompanying diagram and preferably is of wood having a bottomI i also of wood.

As shown in Fig. 2, I provide a bottom comprising a plurality of steps,there being in this particular embodiment two sets of steps which faceone another and which step upwardly and away from a common diameter ofthe bottom of the tank.

The treads of, for example, the left hand set of steps as viewed in Fig.2, are shown at |611 and |20. The faces of said steps are respectively 4shown at [6a and 12a which preferably are slightly inclined.

The right hand set of steps, on the other hand, comprises treads |59 and|211 having faces Ib and lib respectively.

The faces |2a, |2b are of greater area than faces Ia, lBb and preferablyextend outwardly to the inner vertical surfaces of the tank and arefitted thereto.

An island portion I3 may be interposed if desired between the left andright hand sets of steps and may form small troughs I9 and 20respectively therewith. Troughs IS and 20 preferably have inclined sides0r faces as at |8a, ISa and lh, 20a which converge inwardly anddownwardly.

The aerating medium is directed into the container through oricespreferably in the faces |211, Ita, lac and |213, |612, 20a. A pluralityof nozzles I4 of the so-called sweep Variety in faces l2a, |211 areadapted for directing air in a sweeping action over the entire areas oftreads I2C, lid respectively. Nozzles Il are similarly situated relativeto treads ld, ite, and nozzles 2| and 22 direct air into the bottoms oftroughs i9 and 20 respectively through orifices in sides lila, 20a.

A somewhat different conception of the invention is found by consideringthe above described steps as forming a plurality of superposed troughs.For example, as shown in Fig. 2 a plurality of superposed troughs areprovided having inclined sides and having mouths or horizontal openingswhich are in communication with the trough next above it. The troughs,in the form shown, are co-extensive with the bottom area of the tank.

Intense aeration of the calcium chloride liquor may be attained bydirecting air into the troughs by means of nozzles situated preferablyadjacent the bottoms thereof. It is desirable, in the form shown inFigures 1, 2 and 3 to employ 0pposed air streams which are directedtoward one another from opposite sides of the troughs and which areadapted for sweeping the lower surfaces or bottoms thereof.

As shown in Fig. 2, a primary trough |2 is constituted by a pair ofinclined side portions IZa, |219 which are angularly disposed relativeto the vertical axis of the tank and converge downwardly, that is, themouth of the trough flares upwardly and outwardly, thereby causing anysolid matter in the tank which strikes said sides to slide downwardlytoward the center of the reaction vessel.

The above mentioned side portions |2a, |2b are tted to the cylindricalinner surface of the tank as shown in Fig. 1. The bottom of the primarytrough |2 is indicated at |20, |2101 and preferably constitutes flathorizontal surfaces.

The aeration medium such as air is conducted into the primary trough |2by suitable conduits as at I3 which .pass down the inner vertical sidesof the vessel and are, as here shown, in communication with a manifoldIlla situated preferably above the reaction vessel. The manifold la maybe connected by means of a master conduit i5 to a suitable source ofcompressed air which may be controlled by suitable pumping means.

It is desirable in order to accomplish a complete and effectivedistribution of air over the floor or bottom of the primary trough toemploy suitable nozzles which will increase the discharge velocity ofthe air and in effect squirt same over said trough floor.

Such nozzles preferably aredischarge' orifices which, for example,areafbout- 6 in length and about 13-6" in width.

The `nozzles I4, I-I-i andi 2-2` are preferably' closely spacedwherebyabout 90`%of the-length of-"each side of* the trough along thebottomV thereof is directly supplied with` air.; Thosev nozzles, forexample, adjacentY side Ii2`a are*x adaptedl for sweepingV air overthebottom portion I2`c= and the oppositeH group off nozzlesadjacent side|215L areada-pted for'sweepingV air=over the bottom portion I2`d.

A secondary trough is provided at- If6`1 having sides IB'a and |165. Themouth-ofthe-secondary trough I6 is formed in the'bottom of theprimarytrough- I-2. Th'evsides IBaand lbiare preferably inclined substantiallyparallel and in spaced re lation tothe sides I2a and'- I-2b of troughI2- and have formed therein a plurality of orifices I6`c through whichair isfdirected into the trough |6. A plurality of nozzles I'Iareprovidedon opposite sides of the trough' I6- along the bottom thereofwhich are adapted for directing air across the portions IGd and' I6ecomprising respectively the left and right hand" bottom areas (Fig. 2)of trough I 6. The` opposedl air streams from the nozzles |11 maymeetand jointly aerate` the central portion of the bottom of trough I6*indicated atl. Thus theentire flooroff the trough Iii-may befullyaerated` by the action of theair issuing from the nozzles |11 InVorder` further topromote properl aeration, additional troughs may beformed` with the mouths thereof in the bottom of thetrough I6 as at I-llandt2ll.y These two troughs I8, 20, in the form shown, are considerablysmaller than the troughsthereabovelat I-2 andz I6. In the embodimentshown.in.Figs..1,.2.and 3. the troughs I9, preferably are of triangularcross-section, that is, of V-shaped cross-section with the open end ofthe V comprising the mouth ofthe trough.

Air preferably is directed@ into-the trough It and 20 through nozzles:2r|4 and 22; respectively (Fig. 3). The nozzles 2| and 22 are analogousto the nozzles I4 and I'I. Suitable orifices for thenozzles 2|` and 22may be formed within the inclinedsides-fof the troug-hsl I9`\and 20asfshown in Fig. 2.

As is well illustrated in Fig. 2, streams of aerating gas such as airare directed into the vessel I0 laterally thereof by means of horizontalnozzles, thereby minimizing the possibility of clogging or closing theair nozzles with metallic copper or slurry.

The nozzles Il, 2| and 22 are respectively connected to conduits I'Ia, 2Ia and 22a which are in communication with manifold I4a in a manneranalogous to conduit I3.

As illustrated in Figs. 1 and 3, nearly the entire bottom region of thereaction vessel I0 is employed for a reaction chamber, i. e., about 90%thereof is so employed. A small compartment within the tank is formed at23 for other than reaction purposes by means of a partition 24 whichpreferably is of perforated Wood. The partition 24 is designed toprotect tank outlet 25 from being clogged by metallic copper which isplaced within the reaction portion of the vessel.

AL secondE embodiment offy the invention is illusIn trated4in1Fig;.2acomprising apl'uralityof paralleli troughs each havingpreferably aVf-sha-ped' crosssectional area. Sucht paralleli troughs' may be formed,for example, by suitablefwoodenimembers` inclusive'. These troughs mayfbel formed by, for` example, live parallel' wooden` members- 32-3Binclusive which preferablyare of equilateral' triangular crosseseotionalshape each having anl edge of aboutJSf". Membersl', 38?' may be2provided which complete the troughslacting in ooopera-tion respectivelywith the triangular memm bers 321i andl 36.'

lffdesired, theba'sesV` off all of the; above merr-l tioned woodenmembers 32--36` and- Bfl, 38 may" be plaeed'ilushi upon the bottom II oftlietarrltr |01. However, itlis: preferable for said. members:

toA be stepped inthe-manner shown in Fig; 2d, for example; wherein thecentral member 34-onlyf is upon said bottom IVI andA successive pairs ofsuch members are placed upon successivelyhigher levels. For exampley thepair 33, 35- may be secured: at' a rst level. rI-he pair 32, 38" maybe's'ecuredat a second level and the outer members- 31, 38C may besecuredat al thirdandhigher. level.

B'y means ofthe stepped arrangementfof the' above described members32e-3S and` 37.12, 38, it is possible i toeliminatey the exposure of'andi inl-- crease the number of air conduits. which pass parallel toithebottom I|`- and beneath all of" said members except 34. For example, asshow-nin Fig. 2, the horizontal portionsof-` the air conduits at thevarious levels are in steppedI relationship In ftheopenation ofthereaction vesseldes'cribed,

above, it periodically becomesnecessary to clean. the residue therefrom;This is constituted. by undissolved copper and by waste material. It hasbeeny found much more convenient to: clean the bottom' oflthetankillustrated in Fig. 2. thanzthe bottom; illustratedi inl. lfig. 211;.largely because.l of the horizontal `fiat'` bottoms of: the troughs;show-nf in the. former' gure. l\.fLoreov.er, better` access is.k

attainedxto the horizontal sectionsfofs theair. con duits and thenozzles therefor.

In the form of the invention shown, for example, in Figs. 1 and 3, thesteps and troughs are generally of oblong shape and are parallel.However, of course, it is possible to have troughs or basins of circularconformation rather than oblong. Moreover, instead of employing thetrough arrangement of Fig. 2 wherein the bottom is stepped upwardly fromthe center thereof on each side of said center, it is possible tocommence said step at one side of the reaction vessel, for example, theleft side as viewed in Fig. 2, and the steps may progressively risetherefrom to the right side of the container as viewed in said Fig. 2.

The operation of the reaction vessel in general in accordance with myinvention may be as follows: Copper scrap, for example, as blocks ofcompressed copper wire, are placed in the troughs. A reaction liquor ofthe same concentration and volume as above described is added andsubjected to aeration preferably at a rate of 350 cubic feet per minuteor about 121/2 cubic feet for each square foot of bottom area.

Employing a "semi-continuous method of operation wherein a predeterminedpart of the liquor and product, such as 20% to 40%, is periodicallywithdrawn and additions of liquor and copper are periodically made, ahigh average output capacity for a single tank is secured.

The operation of the embodiment of Fig. 2 is analogous to that of Fig.2a in that any settling of the product or precipitate (copperoxychloride) is directed to the bottom of a trough. For example, to theat surface |20 which constitutes a portion of the bottom of trough I2,The air stream issuing from the nozzle i4 will immediately agitate andrecirculate the precipitate. Also, any metallic copper upon said surfaceI2C will be subjected to the air stream which sweeps thereacross andthereby is in direct contact with the metal, thus aiding in the chemicalreaction with the liquor and preventing a coating of said metalliccopper by the slurry or precipitate.

While the invention has been described With respect to certain preferredexamples which have given satisfactory results, it will be understood bythose skilled in the art after understanding the invention that variouschanges and modifications may be made without departing from the spiritand scope of the invention, and it is intended, therefore, in theappended claims to cover all such changes and modications.

What is claimed as new and is desired to be secured by Letters Patentis:

1. A process for producing copper oxychloride comprising, causing aliquor made up of calcium chloride and ammonium chloride to react withpieces of .metallic copper of substantial size in an aqueous solution ina reaction vessel, aerating said solution by directing a plurality ofair streams therein at a plurality of levels near the bottom of thevessel, withdrawing at predetermined intervals a portion of the contentsof the vessel, replacing the withdrawn contents with metallic copper andsubstantially an equal volurne of said liquor, and filtering out copperoxychloride from the contents withdrawn from the vessel.

2. A process for producing copper oxychloride comprising, causing aliquor made up of calcium chloride and ammonium chloride to react withpieces of metallic copper in an aqueous solution in a reaction vessel,the solution containing approximately four to six parts calcium chlorideand one part of ammonium chloride, aerating said solution by directing aplurality of air streams therein at a plurality of different levelsadjacent the bottom of the Vessel, periodically withdrawing from aboutone-fifth to two-fifths of the contents of the vessel, replacing thecontents withdrawn with copper and substantially an equal volume of saidliquor, and ltering out copper oxychloride from the contents withdrawnfrom the vessel.

3. A process for producing copper oxychloride comprising, causing aliquor made up of calcium chloride and ammonium chlorlde to react withpieces of metallic copper of substantial size in an aqueous solution ina reaction vessel, aerating said solution by directing a plurality ofair streams forcefully therein at a plurality of levels near the bottomof the vessel, such copper oxychloride forming a slurry7 in such vesselwhich tends to settle, one or more of such streams striking saidmetallic copper with force sufficient to remove slurry which has settledthereon, Withdrawing at predetermined intervals a portion of thecontents of the vessel, replacing the withdrawn contents with metalliccopper and said liquor, and ltering out copper oxychloride from thecontents withdrawn from the vessel.

4. A process for producing copper oxychloride comprising, causing aliquor made up of calcium chloride and ammonium chloride to react withpieces of metallic copper of substantial size in an aqueous solution ina reaction vessel, aerating said solution by directing a plurality ofair streams forcefully therein at a plurality of levels near the bottomof the vessel, said streams forcefully striking said copper, withdrawingat predetermined intervals a portion of the contents of the vessel,replacing the withdrawn contents with metallic copper and said liquor,and ltering out copper oxychloride from the contents withdrawn from thevessel.

PHILIP KENNETH ANDERSON.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,162,091 Kuss et al June 13, 1939 2,358,706 Haag et al. Sept.19, 1944 FOREIGN PATENTS Number Country Date 413,722 Great Britain July11, 1934 349,232 Italy June 9, 1937

1. A PROCESS FOR PRODUCING COPPER OXYCHLORIDE COMPRISING, CAUSING ALIQUOR MADE UP OF CALCIUM CHLORIDE AND AMMONIUM CHLORIDE TO REACT WITHPIECES OF METALLIC COPPER OF SUBSTANTIAL SIZE IN AN AQUEOUS SOLUTION INA REACTION VESSEL, AERATING SAID SOLUTION BY DIRECTING A PLURALITY OFAIR STREAMS THEREIN AT A PLURALITY OF LEVELS NEAR THE BOTTOM OF THEVESSEL, WITHDRAWING AT PREDETERMINED INTERVALS A PORTIN OF THE CONTENTSOF THE VESSEL, REPLACING THE WITHDRAWN CONTENTS WITH METALLIC COPPER ANDSUBSTANTIALLY AN EQUAL VOLUME OF SAID LIQUOR, AND FILTERING OUT COPPEROXYCHLORIDE FROM THE CONTENTS WITHDRAWN FROM THE VESSEL.